Binuclear n-heterocyclic polyglycidyl compounds, processes for their manufacture, and their use

ABSTRACT

Diglycidyl and tetraglycidyl compounds are obtained by glycidylating diurethanes obtained from 1 mol of a diisocyanate and 2 mols of a 3-hydroxyalkylhydantoin or 3hydroxyalkyldihydrouracil in a known manner with epichlorohydrin or Beta -methylepichlorohydrin. The new epoxide resins can be cured with the customary curing agents for epoxides to give moulded materials having valuable mechanical and dielectric properties and are above all suitable for use as powder resins, such as fluidised bed powders and compression moulding powders.

United States Patent [191 Habermeier et al.

[451 Feb. 18, 1975 [75] Inventors: Jurgen Habermeier, Pfeffingen;

Daniel Porret, Binningen, both of Switzerland [73] Assignee: Ciba-Geigy Corporaton, Ardsley,

[22] Filed: Nov. 21, 1972 [2]] Appl. No.: 308,625

[30] Foreign Application Priority Data Nov. 24, 197i Switzerland 17126/71 [52] U.S. Cl 260/256.4 C, 260/2 EP, 260/2 N, 260/2 EA, 260/32.8 EP, 260/33.2 EP,

260/33.4 EP, 260/33.6 EP, 260/37 EP,

260/260, 260/309.5, 260/DlG. 24

[51] Int. Cl C07d 51/30 [58] Field of Search 260/309.5, 256.4 C

[56] References Cited UNITED STATES PATENTS 3,679,681 7/1972 Habermeier et al. 260/2564 C Primary ExaminerDonald G. Daus Assistant ExaminerRaymond V. Rush Attorney, Agent, or FirmVincent J. Cavalieri [57] ABSTRACT Diglycidyl and tetraglycidyl compounds are obtained by glycidylating diurethanes obtained from 1 mol of a diisocyanate and 2 mols of a 3-hydroxyalkylhydantoin or 3-hydroxyalkyldihydrouracil in a known manner with epichlorohydrin or B-methylepichlorohydrin. The new epoxide resins can be cured with the customary curing agents for epoxides to give moulded materials having valuable mechanical and dielectric properties and are above all suitable for use as powder resins, such as fluidized bed powders and compression moulding powders.

9 Claims, N0 Drawings 1 V 2 BINUCLEAR N-HETEROCYCLIC POLYGLYCIDYL note hydrogen atoms or lower alkyl radicals with 1 to COMPOUNDS, PROCESSES FOR THEIR 4 carbon atoms or R, and R together denote the tetra- MANUFACTURE, AND THEIR USE methylene or pentamethylene radical; R R,, R and R preferably denote hydrogen atoms or lower alkyl radi- The present invention relates to new, binuclear N- 5 cals with l to 4 carbon atoms and B, and B preferably heterocyclic polyglycidyl compounds of the formula denote hydrogen atoms or glycidyl groups; X,, X,, X,

z c=o 0 B B o o=oz l l 2 O l i l il 1) 011 -0-05 :1 recs-caarcam-zeo-o-cmca-a recs -c0u 2 2 I 2 X n X X3 X3,X X 0 0 wherein A denotes a divalent aliphatic, cycloaliphatic, and X preferably denote hydrogen atoms and X and cycloaliphatic-aliphatic, araliphatic, aromatic or X, preferably each represent a hydrogen atom. a heterocyclic-aliphatic radical, Z, and 2, each represent methyl group, an ethyl group or a phenyl group. a divalent radical of the formula The new N,N'-diglycidyl compounds of the formula 70 (l) are as a rule resins which are viscous to solid at room temperature and which can be processed with 3 customary curing agents for expoxide resins, such as R (1 dicarboxylic acid anhydrides or polyamines, either as o 4 75 they are or in a mixture with reactive diluents, to give R r o g mouldings having good mechanical and electrical properties.

5 In addition to the casting resin field, preferred fields of use are above all applications as powder resins, such w as fluidised bed powders and compression moulding wherein R, and R each denote a hydrogen atom or an powders, aliphatic, cycloaliphatic, araliphatic or aromatic hydro- The new polyepoxides of the formula (I) are manucarbon radical, or wherein R, and R, together form a factured according to methods which are in themselves divalent aliphatic or cycloaliphatic hydrocarbon radiknown. A preferred process according to the invention cal, R and R each denote a hydrogen atom or an ali- 35 for their manufacture is characterised in that in a comphatic, cycloaliphatic, araliphatic or aromatic hydropound of the formula i t" Ff- YCH N Iri-CPPCHOCNHA-NHG*OCHCEl-l-l- N-CH -Y'- (Ha) H n l 2 l I X X 0 0- X X O 0 carbon radical and R and R each represent a hydroor of the formula I '2 C O ()-C----Z Y-ca *N N-CH-CH-O-Cfif-k-WC-O-CH-CH-N N-CH *Y' (11b) 2\/ n|lu'||. 2

H m l I X X 0 Y Y 0 X X u 0 0 gen atom or an alkyl radical, B, and B each denote a wherein A, Z,, 2,, X X X and X have the same hydrogen atom, a glycidyl group or a B-methylglycidyl meaning as in the formula (I) and the radicals Y, Y', group, X, and X, each represent a hydrogen atom or Y and Y' are radicals which can be converted into a methyl group, X, and X denote a hydrogen atom or l,2-epoxyethyl or l-methyl-l ,2 epoxyethyl radicals, the methyl radical, X and X, denote a hydrogen atom, 60 these radicals are converted into expoxyethyl or a methyl radical, ethyl radical or phenyl radical, or X, thy 2- p y thyl radicalsflnd 3, or 2 a 3. t gether denote a trimcthylcne A radical Y. Y, Y" or Y' which can be converted radical or tetramethylene radic linto the LZ-epoxycthyL radical or l-mcthyI-l .2-

n the a e rm a A preferably de filCS all ulicpoxycthyl radical is above all a hydroxyhalogcnocthyl phatic, cycloaliphatic, cycloaliphatic-aliphatic, araliradical which carries the functional groups on different phatic or aromatic hydrocarbon radical or a N- carbon atoms, especially a 2-halogeno-l-hydroxyethyl hctcrocyclic aliphatic radical; R, and R preferably deradical or a 2-halogeno-l-hydroxy-l-methylcthyl radical. Halogen atoms are here especially chlorine or bromine atoms. The reaction is carried out in the usual manner, above all in the presence of agents which split off hydrogen halide, such as strong alkalis, for example anhydrous sodium hydroxide or aqueous sodium hy droxide solution. However, it is also possible to employ other strongly alkaline reagents, such as potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate or potassium carbonate.

A further radical Y, Y, Y", or Y' which can be converted into the l,2-epoxyethyl radical is, for example, the ethenyl radical which can be converted into the l,2-epoxyethyl radical in a known manner, such as, above all, by reaction with hydrogen peroxide or peracids, for example peracetic, perbenzoic or monoperphthalic acid.

The starting substances of the formulae ("0) or (llb) are obtained in a manner which is in itself known. Thus it is possible, for example, to react a diurethane of the wherein A, Z Z X X ,x and X have the same meaning as in the formula (I), with a compound of the formula YCH Hal, wherein Hal represents a hydrogen atom and Y has the abovementioned meaning. Preferably, the compound of the formula (H1) is reacted with an epihalogenohydrin or B-methylepihalogenohydrin, above all epichlorohydrin or B-methylepichlorohydrin, in the presence of a catalyst, such as especially a tertiary amine, a quaternary ammonium base or a quaternary ammonium salt. Suitable catalysts for the addition of epichlorohydrin or B-methylepichlorohydrin are above all tertiary amines, such as triethylamine, tri-n-propylamine, benzyldimethylamine, N,N'-dimethylaniline and triethanolamine; quaternary ammonium bases, such as benzyltrimethylammonium hydroxide; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium acetate and methyltriethylammonium chloride; hydrazines having a tertiary nitrogen atom, such as l,l-dimethylhydrazine, which can also be employed in the quaternised form; alkali halides, such as lithium chloride, potassium chlo-. ride and sodium chloride, bromide or fluoride; also ion exchange resins with tertiary or quaternary amino groups, and also ion exchangers with acid amide groups. Basic impurities which can occur in technical commercially available forms of the starting compounds can also act as catalysts. In such cases it is not necessary especially to add a catalyst.

Depending on the molar ratio of the compound of the formula Y-CH- -Hal to the diurethane of the formula (III). and depending on the radical A, 2 to 4 mols of the compound YCH Hal are added to 1 mol of diurethane. The NH groups present in the heterocyclic ring in general react more easily than the active hydrogens of the urethane groups, so that when using approximately 2 mols of compound YCH Ha l per 1 mol of diurethane compounds, of the'=formula ll a are as a rule first produced. Compounds of the formula ll b are above all formed if a stoichiometric excess of the compound YCH Hal is employed and additionally the radical A is an aromatic radical or the urethane groups -CONH are directly bonded to aromatic rings.

A preferred embodiment of the process consists, for example, of reacting an epihalogenohydrin or B-methylepihalogenohydrin, preferably epichlorohydrin or ,B-methylepichlorohydrin, in the presence of a catalyst, such as preferably a tertiary amine, a quaternary ammonium base or a quaternary ammonium salt, with a diurethane of the formula (III), and in a second stage treating the resulting product containing halogenohydrin groups with agents which split off hydrogen halide. In these reactions, the procedure described above is followed, and the compounds mentioned above can be used as catalysts for the addition of epihalogenohydrin or B-methylepihalogenohydrin or for the dehydrohalogenation of the abovementioned compounds. Particu- (III) larly good yields are obtained if an excess of epichlorohydrin or B-methylepichlorohydrin is employed. During the first reaction, before the addition of alkali, a partial epoxidation of dichlorohydrin or of the B-methyldichlorohydrin of the diurethane (lll) already occurs. The epichlorohydrin or B-methylepichlorohydrin which act as hydrogen chloride acceptors have then been partially converted into glycerine-dichlorohydrin or into B-methylglycerine-dichlorohydrin.

The symmetrical diurethanes of the formula (lll) can be manufactured by addition of 1 mol ofa diisocyanate of the formula 0 =C=NAN=C=O (IV) to 2 mols of a N-heterocyclic monoalcohol of the formula l f H mt N-CZI.-G-0II (Va) V l l or of the formula llN NCH '"C'TOH I Diurcthanes of the formula (III) of unsymmetrical structure can be obtained, for example, by first adding 1 mol of a diisocyanate (IV) to 1 mol ofa heterocyclic monoalcohol of the formula (Va) and adding the resulting intermediate product, in a second stage, to 1 mol of a heterocyclic monoalcohol (Vb) which is different from the monoalcohol (Va).

The addition reaction is as a rule carried out at elevated temperature, for example at 60200C, with exclusion of atmospheric moisture, and appropriately in the absence of solvents.

Possible diisocyanates of the formula (IV) are those of the aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic-aliphatic series.

The following may be mentioned as diisocyanates of the aliphatic, cycloaliphatic and araliphatic series: ethylenediisocyanate, trimethylenediisocyanate, tetramethylenediisocyanate, hexamethylenediisocyanate, decatnethylenediisocyanate, 2,2,4- and 2,4,4- trimethylhexamethylenediisocyanate or their technical mixtures; diisocyanates of the formula OCN-Y-NCO wherein Y denotes the hydrocarbon radical ofa dimerised fatty alcohol which is hydrogenated ifappropriate; cyclopentylene-l,3-diisocyanate, cyclohexylene-l,4-, -l,3or -l,2-diisocyanate, hexahydrotoluylene-2,4 or -2,6-diisocyanate, 3,5,5-trimethyl-3-isocyanatomethylcyelohexane-l-isocyanate isophoronediisocyanate); dicyclohexylmethane-4,4'- diisocyanate; o-, mand p-xylylene-a,a-diisoeyanate.

As diisocyanates of the aromatic series there may be mentioned: toluylene-2,4-diisocyanate, toluylene-2,6- diisocyanate or their technical mixtures; diphenylmethane-4,4'-diisocyanate, naphthalenel ,S-diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 3,3'-dimethyl-biphenyl-4,4-diisocyanate, 3,3-dimethoxy-4,4-diphenyldiisocyanate, 3,3-dichloro-diphenyl-4,4-diisocyanate, 4,4'-diphenyldiisocyanate, diphenyldimethylmethane- 4,4-diisocyanate, p,p-dibenzyl-diisocyanate and phenylene-l ,4-diisocyanate; phenylene-l .3- diisocyanate and 2,3,5,b-tetramethyl-p-phenylenediisocyanate; and the uretdione-diisocyanates obtainable by dimerisation of aromatic diisocyanates, such as, for example, of 2,4-toluylenediisocyanate, for example l,3-bis-(4'-methyl-3'-isocyanato-phenyl-)-uretdione of the formula N,N '-di-( 4-methyl-3-isocyanato-phenyl )-urea.

As diisocyanates of the heterocyclic-aliphatic series.

there may be mentioned: 1,3-di-(y-isoeyanatopropyl)- hydantoin, l ,3-di-(y-isocyanatopropyl l ,S-diazaspiro- (4.4)nonane-ZA-dione and l,3-di-(yisoeyanatopropyl I ,3-diaza-spiro-(4.5 )-decane-2,4-

dione, l,3-di-t'y-isocyanatopropyl)-5,5-dimethyl-5,6-

dihydrouracil and l,3-di-(y-isocyanatopropyl)-6-methyl-5,6-dihydrouracil; 1,1 '-methylene-bis-(3y isocyanatopropylhydantoin); l,l-methylene-bis-(3-yisocyanatopropyl-S,S-dimethyl-hydantoin 1,1- methylene-bis-(3-y-isocyanatopropyl-5-methyl5- ethylhydantoin); bis-( 1 '-y-isocyanatopropylhydantoinyl-3')-methane; l,2-bis-( 1-y-isocyanatopropyl-5',5'- dimethylhydantoinyl-3 )-ethane; l,4-bis-( l '-'yisocyanatopropyl-S'-methyl-5-ethyl-hydantoinyl-3)- butane; l,6'bis-( l --y-isocyanatopropyl-5- isopropylhydantoinyl-3')-hexane; l,l2-bis-( l '-yisocyanatopropyl-5,5'-pentamethylenehydantoinyl- 3)-dodecane and ,8, B-bis-(l-'y-isocyanatopropyl- 5,5-dimethylhydantoinyl-3)-diethyl-ether.

The monalcohols of the formulae (Va) and (Vb) are obtained in a known manner by reacting 1 mol of a mononuclear N-heterocyclic compound of the general formula at ar rat NH mt i it a ll 0 (VIa) o (VIb) wherein Z and Z have the same meaning as in the formula (l), with 1 mol of a monoepoxide of the formula wherein X X X and X have the same meaning as in the formula (I), in the presence ofa suitable catalyst.

In the reaction of hydantoins and dihydrouracils with a monoepoxide ofthe formula (Vlla) or Vllh), the acid NH group in position 3 of the ring first reacts. It is therefore possible to react the more strongly acid NH group substantially quantitatively with the monoepoxide before the more weakly acid or practically neutral NH group has reacted significantly. If therefore the reaction which leads to the monohydroxy compound is interrupted at the right moment (testing for the consumption of about 1 mol of monoepoxide per mol of the N-heterocyclic compound (Vla) or (Vlh)), a compound of the formula (Va) or (Vb) is obtained as the main product.

The addition of a monoepoxide to the NH group in the 3-position of the N-heterocyclic compound of the formula (Vla) or (Vlb) can be carried out in the presence of either acid or alkaline catalysts, a slight stoichiometric excess of the monoepoxide being employed as a rule.

Preferably, alkaline catalysts such as tetraethylammonium chloride or tertiary amines, are used in the manufacture of monoalcohols of the formulae (Va) or (Vb). However, alkali halides, such lithium chloride or sodium chloride, can also be used successfully for this addition reaction; the reaction also takes place wihout catalysts. I

The mononuclear N-heterocyclic compounds of the formulae (Vlu) or (Vlb) used for the manufacutre of the alkeneoxide addition products of the formulae (Va) or (Vb) respectively are above all hydantoin, hydantoin derivatives, dihydrouracil and dihydrouracil derivatives.

Hydantoin and its preferred derivatives correspond to the general formula wherein R and R each denote a hydrogen atom or a lower alkyl radical with l to 4 carbon atoms, or wherein R and R together form a tetramethylene or pentamethylene radical. Hydantoin, methylhydantoin, 5-methyl-5-ethylhydantoin, 5-npropylhydantoin, 5 -isopropyl-hydantoin, 1,3- diazaspiro(4.5 )-decane-2,4-dione, l,3-diazaspiro(4.4)nonane-2,4dione and preferably 5,5- dimethyl-hydantoin may be mentioned.

Dihydrouracil (=2,4-dioxo-hexahydropyrimidine) and its preferred derivatives correspond to the general formula 0. n c 1m NH wherein R and R both denote a hydrogen atom or identical or different alkyl radicals, preferably alkyl radicals with l to 4 carbon atoms, and R and R independently of one another each denote a hydrogen atom or an alkyl radical.

Preferably, in the above formula, the two radicals R and R denote methyl groups, R denotes a hydrogen atom or a lower alkyl radical with l to 4 carbon atoms and R denotes a hydrogen atom. 5,6-Dihydrouracil, 5,S-dimethyl-S,6-dihydrouracil (2,4-dioxo'5,5- dimethylhexahydropyrimidine) and 5,5-dimethyl-6- isopropyl-5,o-dihydrouracil (2,4-dioxo-5,5-dimethyl-6- isopropylhcxahydropyrimidine) may be mentioned.

As monoepoxides of the formulae (Vllu) or (Vllh) which are added onto the N-heterocyelic compounds of the formulae (Vlu) or (Vlh) respectively to form the N-heteroeyclic monohydroxy compounds ofthe formulae (Va) or (Vb) respectively, there may he mentioned: ethylene oxide (ethene oxide), propylene oxide (propene oxide), l,2-butene oxide, 2,3-hutene oxide, styrene oxide, l,2-cyclopentene oxide and 1,2- cyclohexene oxide.

A preferred sub-category of N-heterocyclic monohydroxy compounds which are employed as starting substances hence correspond to the formula wherein X and X have the same meaning as in the formula (l) and wherein R and R have the same meaning as in the formula (Vlll). 3-(2'-Hydroxy-ethyl)-5,5- dimethylhydantoin, 3-(2'-hydroxy-n-propyl)-5,5- dimethylhydantoin, 3-(2'-hydroxy-n-butyl)-5,5- dimethylhydantoin, 3-(2'-hydroxy-2'-phenylethyl)-5,5- dimethylhydantoin, 3-(2-hydroxy-n-propyl)-5,5-tetramethylene-hydantoin and 3-(2-hydroxy-1,2- tetramethylene)-5,5-dimethylhydantoin may be mentioned.

A further preferred sub-category of N-heterocyclic monohydroxy compounds which are employed as starting substances correspond to the formula wherein X and X have the same meaning as in the formula (l) and wherein R R R and R have the same meaning as in the formula (lX). 3-(2-Hydroxy-ethyl)- 5 ,5dimethyl-6'isopropyl-5 ,o-dihydrouracil, 3-( 2 hydroxy-n-propyl)-5,5-dimethyl-6-isopropyl-5,6- dihydrouracil, and 3-(2-hydroxy-2-phenyl)-5,5- dimethyl-6-isopropyl-5,5-dihydrouracil, may be mentioned.

The new polyglycidyl compounds of the formula (1), according to the invention, react with the customary curing agents for polyepoxide compounds and can therefore be crosslinked or cured by addition of such curing agents, analogously to other polyfunctional epoxide compounds or epoxide resins. Basic or acid compounds can be used as such curing agents.

As suitable curing agents there may, for example, be mentioned: amines or amides, such as aliphatic, cycloaliphatic or aromatic, primary, secondary and tertiary amines, for example monoethanolamine, ethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, triethylenctctramine, tetraethylenepentamine, N,N-dimethylpropylenediamine-l,3, N,N diethylpropylenediamine- [,3, bis-t4-ami'no-3-methyl-cyclohexyl)-methane, 3,5,- 5-trimethyl-3-(aminomethyll-cyclohexylamine (isophoronediame"), Mannich bases, such as 2,4,6- tris-(dimethylaminomethyl)-phenol; m-

phenylenediamine, p-phenylenediamine, bis-(4- aminophenyl)-methane, bis-(4-aminophenyl)-sulphone and m-xylylenediamine; N-(Z-aminoethyl)-piperazine; adducts of acrylonitrile or monoepoxides, such as ethylene oxide or propylene oxide, to polyalkylenepolyamines, such as diethylenetriamine or triethylenetetramine; adducts of polyamines, such as diethylenetriamine or triethylenetetramine in excess, and polyepoxides, such as diomethanepolyglycidyl-ethers; ketimines, for example from acetone or methyl ethyl ketone and bis(p-amino-pehnyl)methane; adducts of monophenols or polyphenols and polyamines; polyamides, especially those from aliphatic polyamines, such as diethylenetriamine or triethylenetetramine, and dimerised or trimerised unsaturated fatty acids, such as dimcrised linseed oil fatty acid; polymeric polysulphides dicyandiamide, aniline-formaldehyde resins, polyhydric phenols, for example resorcinol, 2,2-bis-(4- hydroxyphenyl)propane or phenol-formaldehyde resins; boron trifluoride and its complexes with organic compounds, such as BF -ether complexes and BE,- amine complexes, for example BF -monoethylamine complex; acetoacetanilide-BF complex; phosphoric acid: triphcnylphosphite; polybasic carboxylic acids and their anhydrides, for example phthalic anhydride, A tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3,6- endomethylene-N-tetrahydrophthalic anhydride, methyl-3,fi-endomethylene-A-tetrahydrophthalic anhydride methylnadic anhydride), 3,4,5,6,7,7 hexachloro-3,6-endomethylene-N-tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, azelaic anhydride, sebacic anhydride, maleic anhydride, dodecenyl-succinic anhydride; pyromellitic dianhydride or mixtures of such anhydrides.

Curing accelerators can furthermore be employed in the curing reaction; when using polyamides, dicyandiamide, polymeric polysulphides or polycarboxylic acid anhydridcs as curing agents, suitable accelerators, are, for example, tertiary amines, their salts or quaternary ammonium compounds, for example 2,4,6-tristdimethylaminomethyl)-phenol, bcnzyldimethylamine, Z-ethyl-4-methyl-imidazole, 4-amino-pyridine and triamylammonium phenolate, and also alkali metal alcoholates, such as, for example, sodium hexanetriolate. In the amine curing reaction, monophenols or polyphenols, such as phenol or diomethane, salicylic acid or thiocyanates, ccan for example be employed as accelerators,

The term curing" as used here denotes the conversion of the abovementioned polyepoxides into insoluble and infusible, crosslinked products, and in particular, as a rule, with simultaneous shaping to give mouldings, such as castings, pressings or laminates and the like, or to give sheet-like structures," such as coatings, coverings, lacquer films or adhesive bonds.

Depending on the choice of the curing agent, the curing reaction can be carried out at room temperature, (18-25C) or at elevated temperature (for example 5(ll 80C).

The curing can. if desired, also be carried out in 2 stages, by first prematurely stopping the curing reaction or carrying out the first stage at only moderately elevated temperature, whereby a still fusible and solu- 65 ble, curable precondensate (a so-callcd B-stage)-is obtained from the epoxide component and the curing agent component. Such a prccondcnsate can, for example, be used for the manufacture of Prepregs, compression moulding compositions or sintcring powders.

A further subject of the present invention are therefore curable mixtures which are suitable or the manufacture of mouldings, including sheet-like structures, and which contain the polyglycidyl compounds according to the invention, optionally together with other polyepoxide compounds and also curing agents for epoxide resins, such as polyamines or polycarboxylic acid anhydrides.

The polyepoxides according to the invention or their mixtures with other polyepoxide compounds and/or curing agents can furthermorebe mixed, in any stage before curing, with customary modifiers, such as extenders, fillers and reinforcing agents, pigments, dyestuffs, organic solvents, plasticisers, flow control agents, agents for conferring thixotropy, flameproofing substances and mould release agents.

As extenders, reinforcing agents, fillers and pigments which can be employed in the curable mixtures according to the invention there may, for example, be mentioned: coal tar, bitumen, glass fibres, boron fibres, carbon fibres, asbestos fibres, natural and synthetic textile fibres, such as polyester fibres, polyamide fibres and polyacrylonitrile fibres; polyethylene powder and polypropylene powder; quartz powder; mineral silicates, such as mica, asbestos powder and slate powder; kaolin, aluminium oxide trihydrate, chalk powder, gypsum, antimony trioxide, bentones, silica aerogel, lithopone; baryte, titanium dioxide, carbon black, graphite, oxide pigments, such as iron oxide, or metal powders, such as aluminium powder or iron powder.

Suitable organic solvents for modifying the curable mixtures are, for example, toluene, xylene, n-propanol, butyl acetate, acetone, methyl ethyl ketone, diacetonealcohol, ethylene glycol monomethyl ether, monethyl ether and monobutyl ether.

As plasticisers for modifying the curable mixtures, dibutyl phthalate, dioctyl phthalate and dinonyl phthalate, tricresyl phosphate, trixylenyl phosphate and also polypropylene glycols can, for example, be employed.

As flow control agents when employing the curable mixtures, especially in surface protection, silicones, cellulose acetobutyrate, polyvinylbutyral, waxes, stearates and the like (which in part are also used as mould release agents) may, for example, be added.

Particularly for use in the lacquer field, the polyepoxide compounds according to the invention can furthermore be partially esterified in a known manner with carboxylic acids such as, in particular, higher unsaturated fatty acids. lt is furthermore possible to add other curable synthetic resins, for example phenoplasts or aminoplasts, to such lacquer resin formulations.

The curable mixtures according to the invention can be manufactured in the usual manner, with the aid of known mixing equipment (stirrers, kneaders, rolls and the like).

The curable epoxide resin mixtures according to the invention are above all employed in the fields of surface protection, the electrieal industry, laminating processes and the building industry. They can be used in a formulation suited in each case to the special end use, in the unfilled or filled state, optionally in the form of solutions or emulsions, as paints, lacquers, compression moulding compositions, sintcring powders, dipping resins, casting resins, injection moulding formulations, impregnating resins and binders, adhesives, tool resins,

gates.

In the examples which follow, unless otherwise stated, parts denote parts by weight and percentages denote percentages by weight. The relationship of parts by volume to parts by weight is as to the millilitre to the gram.

In order to determine the mechanical and electrical Found: Calculated:

The proton-magnetic resonance spectrum (60 Mc- HNMR, recorded in CDCl,,, against tetramethylsilane (TMS) as the internal standard) shows, through the presence of, inter alia, the following signals, that the properties of the curable mixtures described in the ex product essentially has the following formula:

amples which follow, sheets of size 92 X 41 X 12 mm were manufactured for determining the flexural strength, deflection, impact strength and water absorption. The test specimens, X 10 X 4 mm) for deter- 20 mining the water absorption and for the flexural test and impact test (VSM 77,103 and VSM 77,105 respectively) were machined from the sheets.

For determining the heat distortion point according to Martens (DlN 53,458), test specimens of size X 15 X 10 mm were cast in each case.

To test the arcing resistance and tracking resistance (VDE 0303), sheets of size 120 X 120 X 4 mm were CH 3 1-8 a s CH (2x 0 O-CH-) I H CH 8 2.15: 3 H 1 CH group bonded to the aromatic ring 5 3.60 8 multiplets: 6H (N-CH -CH -O) Structural formula ea 0 a H C H O u 2. Diurethane from 1 mol fo isophorone diisocyanate" and 2 mols of 3-(2-hydroxy-n-propyl)-5,5- dimethylhydantoin 372 g of 3(2'-hydroxypropyl)-5,5-dimethylhydantoin (1.84 mols) are reacted with 201 g (0.909 mol) of 3,5,5-trimethyl-3-isocyanatomethyI-cyelohexane-l-isocyanate (isophoronediisocyanate") analogously to Instruction A l.

The reaction temperature is about l00/130C and the reaction time is 3 hours. The reaction takes place slightly exothermically. The adduet is worked up as described in Instruction A. l.

The crude adduct, which melts at -130C, is obtained in quantitative yield. The product can be purified by recrystallisation. It consists of the diurethanc of the formula CH CH 'j O v. i all CH- CH e-c CH CU A 5 v I 3 1H: IFCH cseo o-n-ca e-- aca 2 n y l I C 0 H terse-circa "N DH! I] u 2 H o f 0 denser, and the resulting paste is heated to 90C whilst 3. Diurethane from 1 mol of hexamethylenestirring. The reaction becomes exothermic and after removal of the heating bath the temperature rises to l 15-l 20C. After the exothermic effect has subsided,

the mixture is stirred for a further hour at 160C. The 65 resulting light brown clear melt is poured out onto a metal sheet to cool. After cooling, the product is broken up and powdered. A light ochre-coloured powder which softens at 116C (Kofler) is obtained. Elementary analysis shows:

diisocyanate and 2 mols of 3-(2-hydroxyethyl)-5.5- dimethyl-6-isopropyl-5,6-dihydrouracil.

10.2 g (0.0447 mol) of 3-(2'-hydroxy-ethyl)-5,5- dimethyl-6-isopropyl-5,-dihydrouracil (melting point 129.4-130.4C) and 3.76 g of 1,6- hexamethylencdiisocyanate (0.02235 mol) are stirred together at C bath temperature to give a homogeneous, clear, colourless melt. In the course thereof, the

internal temperature settles at 128130C. After the yield is finely powdered. It melts at 152C (Mettler FP two and a half hours reaction, the addition is complete 51; 2C/minute).

and the product obtained in quantitative yield is cooled The product essentially consists of the diurethane of to room temperature. A brittle glass results, which can the formula:

on. ca on. I I 3 I i H C-"C=O H CC-C=0 O=CCCh'.. I o H I n 0 J u I I n I 1I"-1C-" *1 "1" 1. H /ll-C1I ({Li'Ofl?" C i 11 CH N Il-CH C 1 CH 1 C, O' \|1H 011 II /I H C C C H CH u CH3 0 0 O easily be ground to give a colourless powder of the fine- 5. diurethane from 1 mol of 4,4-

ness ofdust. The product hasamelting point of58.8C. diisocyanatodiphenylmethane and 2 mols of 3-(2- The proton-magnetic resonance spectrum (60 Me hydroxy-n-propyl)-5,5-pentamethylene-hydantoin. H-NMR recorded in deuterodimethylsulphoxide. O A mixture of 25.2 g of 4,4- against tetramethylsilane as the internal standard) diisocyanatodiphenylmethane (0.1 mol) and 45.3 g of shows inter alia through the presence of the following 3-(2-hydroxypropyl)-5,5-pentamethylenehydantoin signals that the product has the structure shown below: (0.2 mol) is stirred for 4 hours at 190-l92C; thereaf- 8 0.55 1.35 8 methyl groups ter the clear melt is treated as described under A)4. A 8 1.7 2.2 4 methylene groups slightly coloured crystalline powder which melts at 5:311 I 177C (Mettler F? 51; 2C/minute) is obtained in 8:40 6 mcthilcn" gmups' dammed quantitative yieldv The product essentially consists of a 6.95 2 N-H groups the diurethane of the formula 8 8.0 2 N-H groups (i=0 O=G l o H H 0 I I II I u I 1111 11-011 -CH-OG-I-l- O -CZI @ICOCHCH -11 11H \C/ 2 I 2 I 2 \C/ H CH v v 011 n O O The product essentially consists of the diurethane of the formula li V o O H H 0 u n I I 11 )1 EN 11 CH CH oo1-r-(ca --NGOCH CH -11 2 2 2 6 2 2 I H C c CH H-C!' 0 3 H 0 (R 0 O n 0 CH 0 3 5 3 H c CH 3 5 4. Diurethane from 1 mol of 1,3-(y- B. Manufacturing Examples diisocyanatopropyl)-5,5-dimethylhydantoin and 2 mols of 3-(2'-hydroxy-n-propyl)-5,5-dimethylhydantoin. EXAMPLE 1 A mixture of 0.15 mol of 88.5% strength 1,3-(ydiisocyanato-propyl)-5,5-dimethylhydantoin (49.9 g) A mixture of 273.3 g (0.5 mol) of the diurethanc and 0.3 mol of 3 -(2-hydroxy-n-propyl)-5,5- manufactured according to Instruction A. 1. from 1 dimethylhydantoin (55.8 g) is stirred for 2 hours at mol of toluylene-2.4-diisocyanate and 2 mols of 3-(2' 133-137C and is subsequently allowed to continue to hydroxy-n-propyl)-5,5-dimethyl-hydantoin. 1.385 g of react for about4 hours at 157160 C.The hot, clear epiehlorohydrin (15 mols) and 2.5 g of tetraethylmelt is then poured out onto a metal sheet to cool. ammonium chloride is stirred for 45 minutes at C. After cooling, the crude solid obtained in quantitative A slightly cloudy solution is thereby produced.

A vigorous circulatory distillation is now set up at l-140C bath temperature by applying vacuum (60-90 mm Hg) whilst stirring, in such a way that an internal temperature of 60C results. When this circulatory distillation has been set up, 96.0 g of strength aqueous sodium hydroxide solution are added dropwise over the course of 120 minutes whilst stirring vigorously. At the same time, the water present in the reaction mixture is continuously removed from the circulation and separated off.

After completion of the addition of the alkali solution, the distillation is continued until the last traces of water have been removed from the mixture; this requires about 2030 minutes.

2,4-diisocyanate and 2 mols of 3-(2-hydroxy-npropyl)-5,5-dimethyl-hydantoin are treated with 1,925 g of epichlorohydrin (20.8 mols) and with 3.45 g of tetraethylammonium chloride, analogously to the description in Example 1. The dehydrohalogenation with 134.4 g of 50% strength sodidum hydroxide solution and the subsequent working-up also take place on accordance with Example 1.

267.4 g of a light brown, viscous clear resin are obtained (yield: 100% of theory) the resin having an epoxide content of 4.71 equivalents/kg (corresponding to 90.6% of theory); the total chlorine content is 2.5%. The product essentially consists of the tetraepoxide of the formula H. C C ll CH. j 3 5g 5 CH 0 u CH 0 3 C Cll l1--C11 l IL CH 3l"O l 0 "01 "(11 "ll l '-"C1l Ell G (H N U O C u l g u 0 CH 0 The mixture is now cooled to approx. 35C and fil- EXAMPLE 3 tered to remove the sodium chloride produced during the reaction. The filter residue is washed with 100 ml of epichlorohydrin; to remove traces of sodium chlo- 35 405 g (0.68 mol) of the diurethane manufactured acride and of catalyst, the combined epichlorohydrin socording to Instruction A, 2. from 1 mo] of lutions are extracted by shaking with 80 ml of water. After separating off the aqueous layer, the organic phase is concentrated on a rotary evaporator at C under a slight vacuum. Thereafter 50 ml of water are added and the mixture is concentrated, and finally 50 ml of toluene are added and the concentration is completed. The product is then dried to constant weight at C and 10.1 mm Hg.

325 g of a clear, highly viscous, light yellowish epoxide resin (yield: 99.1% of theory) are obtained. The product essentially consists of the diepoxide of the for mula isophoronediisocyanate and 2 mols of 3-(2'-hydroxy-npropyl)-5,5-dimethyl-hydantoin are treated with 1,575 g of epichlorohydrin (l7 mols) and 3.4 g of tetraethylammonium chloride, as described in Example 1.

The dehydrohalogenation with 138 g of 50% strength aqueous sodium hydroxide solution and the working-up and isolation of the reaction product are also carried out in accordance with Example 1.

A solid, clear, brittle, light brown epoxide resin which has an epoxide content of 2.83 equivalents/kg of theory) is obtained in 95.6% yield (459.0 g); the total chlorine content is 1.8%.

the following structure:

A solution of 12.5 g (0.02 mol) of the diurethane manufactured according to Instruction A. 3. from 1 mol of hexamethylenediisocyanate and 2 mols of 3-(2- hydroxyethyl)-5,5-dimethyl-6-isopropyl-5,6- dihydrouracil in 111 g of epichlorohydrin (1.2 mols) is stirred with 0.1 g of tetramethylammonium chloride for minutes under reflux.

Thereafter dehydrochalogenation is carried out with 4.0 g of strength aqueous sodium hydroxide solution according to Example 1. Working-up also takes place analogously to the description in Example 1.

15 g (theory 14.8 g) of a pale yellow, clear, highly viscous resin having an epoxide content of 3.0 epoxide equivalents/kg are obtained. Accordingly, the product mainly consists of the diglycidyl compound of the formula o=cc en I a o I 11 c on o 0 cn EXAMPLE 6 Analogously to Example 1, 61 g (0.0868 mol) of the crude diurethane manufactured according to Instruction A. 5. from 1 mol of 4,4- diisocyanatodiphenylmethane and 2 mols of 3-(2'- hydroxy-n-propyl)-5,5-pentamethylenehydantoin are reacted with 201 g of epichlorohydrin (2.172 mols),

The product is contaminated with a trace of triglycidyl 0.4315 g of tetraethylammonium chloride and 15.98 g

compound or tetraglycidyl compound.

EXAMPLE 5 89.5 g (0.1342 mol) of the crude diurethane manufactured according to Instruction A.A. from 1 mol of 65 1,3-(y-diisocyanatopropyl )-5,5-dimethylhydantoin and 2 mols of 3-(2"hydroxy-n-propy1)-5,5- dimethylhydantoin are treated, analogously to Example of 50% strength aqueous sodium hydroxide solution. The dehydrohalogenation and isolation of the product are also carried out in accordance with Example 1. A viscous resin possessing 2.34 epoxide equivalents/kg (99.8% oltheory) is obtained in 79.9% yield. The product essentially consists of the diglycidyl compound of the following structure:

I I i HC CH C. Examples of Uses EXAMPLE I are mixed in a beaker with the equivalent amounts of hexahydrophthalic anhydride (series A) and isophoronediamine (series B) and cured for to hours light-coloured mouldings having the following properties are obtained:

Flexural strength (VSM 77.103) 8 3 Deflection (VSM 77.103) :2.0

at 140C. The glass transition temperatures were measured on the samples:

Epoxide resin, manufactured Glass transition temperature according to Example C) Series A Series B l 127 I49 2 162 M2 3 I60 171 We claim:

ln1p c[5[reng[h(\ SM 77,10 1 l. A binuclear N-heterocyclic polyglyeidyl com- Heat distortion point according to pound f h f l Martens (DIN 53.458) ;99c

z -c=o o=c-z O B B O O l 2' u l n CH --CCH N N-CH-CHOC NANC OCHCHN N-CH C -CH I I l L X 1 E 2 3 3' 2' A 1' EXAMPLE [I wherein A is tolylene. phenylene, alkylene containing Flexural strength (VSM 77.103) Il.3 kp/mm" Deflection (VSM 77,l03) :3.2 mm

Impact strength (VSM 77,l05) 10.3 cm.kp/cm Heat distortion point according to Martens (DIN 53.458) 126C EXAMPLE III 141 g of the epoxide resin manufactured according to Example 3, having an epoxide content of 2.83 epoxide equivalents/kg, are cured with 60 g of hexahydrophthalic anhydride at 90C in an aluminium mould in 2 hours at 90C 13 hours at 150C. The resulting clear moulding has good mechanical properties.

EXAMPLE [V Two samples (series A and B) of each of the epoxide resins manufactured according to Example I, 2 and 3 2 to 10 carbon atoms Z, and 2 are the same and each represents a divalent radical of the formula wherein each of R,, R R R R and R independently of one another is hydrogen or alkyl of l to 4 carbon atoms or wherein R, and R together is tetramethylene or pentamethylene; B, and B are the same and each is hydrogen, glycidyl, or B-methylglycidyl; X, and X, are the same and each represents hydrogen or methyl; X and X, are the same and each represents hydrogen or methyl; X and X are the same and each represents hydrogen, methyl, ethyl, or phenyl or X and X and X and X together represent trimethylene or tetramcthylene.

2. A binuclear N-heterocyclic polyglycidyl compound according to claim 1 where each of Z, and Z is wherein each of R, and R is hydrogen or lower alkyl wherein each of R R10, R,, and R is hydrogen or lower alkyl of l to 4 carbon atoms.

4. The compound according to claim 1 ofthe formula OH H. C CH 5 \l 3 C I 0 3 "-C H O CH c--c-c c Bn-c it Ill-C E: I" ['3 l I 5 /O\ H --C O-C 2 5 2 N11 CH /CH-CH N\ /NCH Cit-CH m4 c o 5. The compound according to claim 1, of the formula -H C CH 3C\ H310 CH Q 3 o *f 1 l 3 l i 0 I "C CH'" N- CIH-CH N\ /N-CH l-l(.7C-l Cl-I CH N\ CH CH CH c N-- C O C CH 1 ll I 2 l 0 ll 0 OH 0 O l CH 6. The compound according to claim 1, of the formula H C H C i 3 5 0 l CH c-c 0H, 0 B0 on 0 c-c l l 9 11 3 3 l 3 Cl- CH-CH -N\ /NCH CH-OC-NHCI'l /O- CHCH N\ /N*CH -C i-Cl c N-C= a I ll H O 24 9. The compound according to claim I. of the formula 8. The compound according to claim 1, of the formula 

1. A BINUCLEAR N-HETEROCYLIC POLYGLYCIDYL COMPOUND OF THE FORMULA
 2. A binuclear N-heterocyclic polyglycidyl compound according to claim 1 where each of Z1 and Z2 is
 3. A binuclear N-heterocyclic polyglycidyl compound according to claim 1 where each of Z1 and Z2 is
 4. The compound according to claim 1 of the formula
 5. The compound according to claim 1, of the formula
 6. The compound according to claim 1, of the formula
 7. The compound according to claim 1 of the formula
 8. The compound according to claim 1, of the formula
 9. The compound according to claim 1, of the formula 